CN101233096A - Process for producing alpha, beta-unsaturated carboxylic acid - Google Patents
Process for producing alpha, beta-unsaturated carboxylic acid Download PDFInfo
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- CN101233096A CN101233096A CNA2006800283786A CN200680028378A CN101233096A CN 101233096 A CN101233096 A CN 101233096A CN A2006800283786 A CNA2006800283786 A CN A2006800283786A CN 200680028378 A CN200680028378 A CN 200680028378A CN 101233096 A CN101233096 A CN 101233096A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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Abstract
A process for producing an alpha, beta-unsaturated carboxylic acid which comprises oxidizing an olefin or alpha, beta-unsaturated aldehyde in a liquid phase in the presence of a noble-metal catalyst. The process can ensure operational safety in stopping the reaction and prevent the noble-metal catalyst from deteriorating. The process, which is for producing an alpha, beta-unsaturated carboxylic acid by oxidizing an olefin or alpha, beta-unsaturated aldehyde in a liquid phase in the presence of a noble-metal catalyst in a reactor, includes a stoppage step in which an inert gas is supplied to the reactor to stop the oxidation reaction. Thus, an alpha, beta-unsaturated carboxylic acid is produced.
Description
Technical field
Thereby the present invention relates to carry out liquid phase oxidation reaction preparation α, the method for beta-unsaturated carboxylic acid.
Background technology
As α, the preparation method of beta-unsaturated carboxylic acid discloses following method, that is: supply with C3～C6 alkene and oxygen to reactor, in the presence of the activatory palladium metal catalyst, olefin oxide in liquid phase, thereby obtain α, beta-unsaturated carboxylic acid (with reference to patent documentation 1).
Patent documentation 1: the spy opens clear 60-155148 communique
Summary of the invention
Although the method for deactivated catalyst when the reaction beginning has been shown in patent documentation 1, the method that relates to stopped reaction has not been shown.Owing to reasons such as the inspection of equipment, repairings, stopping to supply with C3～C6 alkene and oxygen at the same time comes in the situation of stopped reaction, because after reaction stopped, there was oxygen in the liquid phase portion dissolving of reactor, so might cause the oxidative degradation of noble metal catalyst.In addition, the alkene of the unreacted C3～C6 of gasification and oxygen are partly accumulated at the reactor upper space, partly exist at the reactor upper space under the state of inflammable gas, and then dissolve the oxygen volatilization that is present in the reaction solution, and oxygen concn is risen, and might explode.
The objective of the invention is to, α is provided, the preparation method of beta-unsaturated carboxylic acid, it is in the presence of noble metal catalyst, olefin oxide or α in liquid phase, beta-unsaturated aldehyde, thereby preparation α, the method of beta-unsaturated carboxylic acid, the operational security when this method can be guaranteed stopped reaction prevents the deterioration of noble metal catalyst.
To the effect that of the present invention:
A kind of α, the preparation method of beta-unsaturated carboxylic acid is in reactor, in the presence of noble metal catalyst, by making alkene or α in liquid phase, thereby the beta-unsaturated aldehyde oxidation generates α, the oxidizing reaction of beta-unsaturated carboxylic acid, prepare α, the method for beta-unsaturated carboxylic acid
It is characterized in that, comprise that in above-mentioned reactor supplying with non-active gas makes the operation that stops that above-mentioned oxidizing reaction stops.
A preferred version as the present application is above-mentioned α, the preparation method of beta-unsaturated carboxylic acid, it is characterized in that, in reactor, supply with alkene or α, beta-unsaturated aldehyde, solvent and molecular oxygen, carry out above-mentioned oxidizing reaction continuously, stop in the operation, before supplying with non-active gas, stop the supply of molecular oxygen above-mentioned.Stop in the operation above-mentioned, also can after supplying with non-active gas, stop to supply with alkene or α, beta-unsaturated aldehyde.A scheme that is more preferably is, stops in the operation above-mentioned, and feed speed from non-active gas to reactor that supply with is 1～100 times of feed speed of supplying with molecular oxygen in above-mentioned oxidizing reaction.
A preferred version as the present application is above-mentioned α, the preparation method of beta-unsaturated carboxylic acid, it is characterized in that, stop in the operation above-mentioned, the cumulative volume of non-active gas under 0 ℃, 1 normal atmosphere that supplies in the reactor is 1～1000 times of amount of the reaction solution volume in the above-mentioned reactor.
A preferred version as the present application is above-mentioned α, the preparation method of beta-unsaturated carboxylic acid, it is characterized in that, stop in the operation that the cumulative volume of non-active gas under 0 ℃, 1 normal atmosphere that supplies in the reactor is 1～1000 times of amount of above-mentioned reactor volume above-mentioned.
A preferred version as the present application is above-mentioned α, and the preparation method of beta-unsaturated carboxylic acid is characterized in that, stops in the operation above-mentioned, further supplies with reductive agent to reactor.For example, as above-mentioned reductive agent, can use to be liquid alkene or α, beta-unsaturated aldehyde under the temperature and pressure in reactor.A scheme that is more preferably is to stop in the operation above-mentioned, with the volume V[liter of the reaction solution in the reactor] be benchmark, the amount [gram] that supplies to the reductive agent in the reactor is V * 100～V * 2000.
The present invention is in the presence of noble metal catalyst, olefin oxide or α in liquid phase, and beta-unsaturated aldehyde, thereby preparation α, the method for beta-unsaturated carboxylic acid, the operational security when this method can be guaranteed stopped reaction prevents the deterioration of noble metal catalyst.
Embodiment
Below, the present invention will be described in detail.
In the present invention, in liquid phase, in the presence of noble metal catalyst, with raw material olefin or α, beta-unsaturated aldehyde carries out oxidation by molecular oxygen, generates α, the oxidizing reaction of beta-unsaturated carboxylic acid.By such oxidizing reaction, can high selectivity, prepare α, beta-unsaturated carboxylic acid with high yield.Oxidizing reaction can be carried out with continous way, step arbitrary mode, but from the viewpoint of productivity, preferred continous way.
As alkene, preferred carbon number is 3～6 alkene, can list for example propylene, iso-butylene, 1-butylene, 2-butylene etc.As α, beta-unsaturated aldehyde can list for example propenal, Methylacrylaldehyde, crotonic aldehyde (Beta-methyl propenal), phenylacrolein (beta-phenyl propenal) etc.
The α of preparation, beta-unsaturated carboxylic acid is under the situation of alkene at raw material, is the α that 1 methyl of alkene changes into carboxyl, beta-unsaturated carboxylic acid is α at raw material, under the situation of beta-unsaturated aldehyde, be α, the aldehyde radical of beta-unsaturated aldehyde changes into the α of carboxyl, beta-unsaturated carboxylic acid.Specifically, when raw material is propylene or propenal, vinylformic acid can be obtained, when raw material is iso-butylene or Methylacrylaldehyde, methacrylic acid can be obtained.
As source of molecular oxygen, air is economical, thereby preferred, but also can use purity oxygen or purity oxygen and Air mixing gas, as required, also can use the mixed gas that forms with diluent air such as nitrogen, carbonic acid gas, water vapour or purity oxygen.Preferably supply with molecular oxygen with the pressurized state in the reactors such as autoclave.
There is no particular limitation to solvent used in the oxidizing reaction, can make water; Alcohols such as the trimethyl carbinol, hexalin; Ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK); Organic acids such as acetate, propionic acid, butanic acid, isopropylformic acid, positive valeric acid, isovaleric acid; Organic acid ester such as ethyl acetate, methyl propionate; Hydro carbons such as hexane, hexanaphthene, toluene; Or the like.Wherein, preferred carbon number is that 2～6 organic acid, carbon number are 3～6 ketone, the trimethyl carbinol.Solvent can be a kind, also can be the mixed solvent more than 2 kinds.
Noble metal catalyst contains the precious metal as the catalyzer of oxidizing reaction.Can use for example palladium, platinum, rhodium, ruthenium, iridium, gold and silver, osmium as precious metal.Wherein preferred palladium, platinum, rhodium, ruthenium, iridium and gold, preferred especially palladium.Precious metal can use a kind, and also two or more kinds may be used.
Noble metal catalyst can contain the metal arbitrarily (base metal) beyond the precious metal.As base metal, preferred bismuth, tellurium.Base metal can use a kind, and also two or more kinds may be used.From the viewpoint of catalytic activity, in the metal that contains in noble metal catalyst, non-noble metal ratio is preferably below the 50 atom %.
Noble metal catalyst can be non-supported, also can be loaded.As the carrier that in loaded occasion, uses, for example can list gac, carbon black, silicon-dioxide, aluminum oxide, magnesium oxide, calcium oxide, titanium dioxide and zirconium white etc.Wherein, preferably use gac, silicon-dioxide, aluminum oxide.Carrier can use a kind, and also two or more kinds may be used.The rate that supports of the precious metal in the occasion of supported catalyst, the carrier with respect to before supporting is preferably 0.1～40 quality %, more preferably 1～30 quality %.
In addition, in order to prevent the polymerization of raw material, resultant, preferably in reaction solution, there is the stopper about 1～10000ppm.As stopper, for example can list phenolic compounds such as quinhydrones, p methoxy phenol; N, N ,-di-isopropyl Ursol D, N, aminated compoundss such as N '-two-2-naphthyl p-phenylenediamine, N-phenyl-N '-(1, the 3-dimethylbutyl) Ursol D, phenothiazine; 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxyradical, 4-benzoyloxy-2,2,6,6-tetramethyl piperidine-N-oxyradical compounds such as N-oxyradical; Or the like.Stopper can use a kind, and also two or more kinds may be used.
The condition of oxidizing reaction can suitably be selected according to the solvent and the raw material that use, below optimum condition is described.
Liquid volume in the reactor (note is made the V[liter]) is preferably 10～80% of reactor volume.Temperature of reaction is preferably 30～200 ℃, more preferably 50～150 ℃.Reaction pressure is preferably 0～10MPaG, is more preferably 2～7MPaG.The usage quantity of noble metal catalyst with respect to the liquid in the reactor, is preferably 0.1～50 quality %, is more preferably 0.5～30 quality %, more preferably 1～15 quality %.Noble metal catalyst can use with the state that is suspended in the reaction solution, also can use in the mode of fixed bed.
When carrying out oxidizing reaction continuously, supply with alkene or α continuously, beta-unsaturated aldehyde, solvent and molecular oxygen.Preferably supply with each composition under the following conditions continuously.Raw material olefin or α, the feed rate of beta-unsaturated aldehyde [g/h] is preferably V * 10～V * 500.The feed rate of solvent [g/h] is preferably V * 100～V * 2000.The feed rate of molecular oxygen [g/h] is preferably V * 100～V * 2000.In addition, the feed rate of the unit time of molecular oxygen, raw material olefin with respect to 1 mole or α, beta-unsaturated aldehyde is preferably 0.1～20 mole, is more preferably 0.1～5 mole.
Show the preferred version of the modulator approach of above-mentioned noble metal catalyst below.
At first, with desired order or add precious metal chemical complex and carrier simultaneously, the modulation carrier disperses the dispersion liquid that forms in solvent.Then, in this dispersion liquid, add reductive agent,, precious metal atom is supported on the carrier simultaneously with the precious metal atom reductive.
The precious metal chemical complex that uses during to modulation catalyst does not have particular determination, preferably contains the compound of the precious metal atom of the state of oxidation.The muriate of preference such as precious metal, oxide compound, acetate, nitrate, vitriol, tetrammine and acetylacetonate complex etc. wherein are more preferably muriate, acetate, the nitrate of precious metal.
When modulation contains non-noble metal noble metal catalyst, can and use precious metal chemical complex and non-noble metal metallic compound.For example, in the time of can in liquid phase, reducing precious metal chemical complex, be dissolved in method in this solvent, make and contain base metal in the noble metal catalyst by making non-noble metal metallic compound in advance.
The solvent that uses during as modulation catalyst, preferably water, but the dispersiveness of carrier according to the solvability of precious metal chemical complex and reductive agent and when using carrier also can the independent or multiple alcohol such as ethanol, 1-propyl alcohol, 2-propyl alcohol, propyl carbinol, the trimethyl carbinol that are used in combination; Ketone such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone; Organic acids such as acetate, positive valeric acid, isovaleric acid; Hydrocarbon such as heptane, hexane, hexanaphthene; Deng organic solvent.
The reductive agent that uses during to modulation catalyst does not have particular determination, for example can list, hydrazine, formaldehyde, sodium borohydride, hydrogen, formic acid, formate, ethene, propylene, 1-butylene, 2-butylene, iso-butylene, 1,3-butadiene, 1-heptene, 2-heptene, 1-hexene, 2-hexene, tetrahydrobenzene, vinyl carbinol, methylallyl alcohol, propenal and Methylacrylaldehyde etc.
Reduction temperature, according to the difference of the precious metal chemical complex that uses, reductive agent etc. and difference, but preferably-5～150 ℃, be more preferably 15～80 ℃.Recovery time is preferably 0.1～4 hour, is more preferably 0.25～3 hour, further preferred 0.5～2 hour.
By the noble metal catalyst that reduction is separated out, washings such as preferred water, solvent are to remove the impurity from precious metal chemical complex such as muriate, acetate moiety, nitrate radical, sulfate radical.
The noble metal catalyst that preferred use obtains like this carries out oxidizing reaction.
In the present invention, after carrying out above-mentioned oxidizing reaction, in reactor, supply with non-active gas and make reaction stop (stopping operation).Carrying out continuously in the situation of oxidizing reaction, preferably in stopping operation, before supplying with non-active gas, stopping to supply with molecular oxygen.Like this when stopping oxidizing reaction, by in reactor, supplying with non-active gas, molecular oxygen in the reactor can be driven out of outside the reactor, can avoid oxygen concn in the gas of reactor upper space part to rise causing the danger of exploding, and prevent that molecular oxygen from causing the noble metal catalyst deterioration.
As non-active gas, can list rare gas such as nitrogen, carbonic acid gas or helium, neon, argon gas etc.
The supply position of supplying with non-active gas in the subtend reactor does not have particular determination, but in order to drive the molecular oxygen that exists around the noble metal catalyst out of reactor more effectively, preferably the liquid phase portion in reactor supplies with non-active gas.
Supply to the cumulative volume of non-active gas under 0 ℃, 1 normal atmosphere 1～1000 times of amount of the reaction solution volume in the reactor preferably in the reactor, be more preferably 2～100 times of amounts.In addition, supply to the cumulative volume of non-active gas under 0 ℃, 1 normal atmosphere 1～1000 times of amount of above-mentioned reactor volume preferably in the reactor, be more preferably 2～100 times of amounts.By like this, can make reaction solution and comprise that the interior oxygen concn of reactor of reactor upper space part reduces, deterioration and the explosion hazard that the oxidation of noble metal catalyst causes avoided in realization simultaneously.
And then when carrying out oxidizing reaction continuously, the speed to reactor supply non-active gas from can fast the molecular oxygen in the reactor being driven out of the viewpoint of reactor, preferably 1～100 of the feed speed of molecular oxygen times, is more preferably 1～10 times.In addition, in stopping operation, can after supplying with non-active gas, stop alkene or α, the supply of beta-unsaturated aldehyde.
By the oxygen concn in the reactor that supply realized of non-active gas, be preferably below the 10 capacity %, be more preferably below the 1 capacity %, more preferably below the 0.01 capacity %.
The non-active gas of in reactor, supplying with, preferably supply to always stop operation and finish till.Stopping before operation finishes, can be continuously or supply with non-active gas intermittently.For reaction is stopped, preferably supplying with non-active gas continuously.
In stopping operation, preferably further supply with reductive agent to reactor, noble metal catalyst is in the reducing atmosphere on every side.The amount [gram] of the reductive agent of supplying with, the viewpoint of the deterioration that causes from the oxidation that prevents noble metal catalyst is a benchmark with the volume of the reaction solution in the reactor (note is made the V[liter]), is preferably V * 100～V * 2000, is more preferably V * 110～V * 1000.
As reductive agent, can list the reductive agent that uses when above-mentioned catalyzer is modulated, but preferred alkenes or α, beta-unsaturated aldehyde.When behind stopped reaction, beginning to react once more, can carry out the viewpoint that stable reaction begins to operate under the condition that does not influence main reaction sets out, be more preferably preparation α, the raw material olefin of the oxidizing reaction of beta-unsaturated carboxylic acid or α, beta-unsaturated aldehyde is as reductive agent.In addition, from making noble metal catalyst the liquid phase be in the viewpoint of reducing atmosphere by supplying with reductive agent, preferably be liquid reductive agent under the temperature and pressure in reactor, be liquid alkene or α, beta-unsaturated aldehyde down particularly preferably in the temperature and pressure in the reactor.
Concentration to the reductive agent in the reaction solution does not have particular determination, but from when oxidizing reaction is begun once more, carrying out the viewpoint that stable reaction begins to operate, and then under the situation that also proper energy reduces that does not make in the reactor, preventing the viewpoint of the oxidation of noble metal catalyst, preferred 0.1～50 quality % is more preferably 1.0～20 quality %.
Preferably after in reactor, beginning to supply with non-active gas, or with beginning simultaneously, the temperature in the reactor is reduced.Be more preferably at beginning in addition after reactor is supplied with non-active gas and begun to supply with reductive agent, reduce the temperature in the reactor.
After oxygen concn in reactor and temperature fully reduce, make the pressure recovery normal pressure in the reactor, finish to stop operation.Preferably the temperature in reactor reaches below 50 ℃, and the oxygen concn in the reactor reach 1 volume % following when, with the pressure recovery in the reactor to normal pressure.
Embodiment
Below, further describe the present invention by embodiment, but the present invention is not limited by these embodiment.
(catalyzer modulation)
The acid chloride (NE ケ ミ キ ヤ Star ト society system) of 48g is dissolved among the mixing solutions 2640g of the positive valeric acid of 88 quality % and 12 quality % water.This solution is transferred in the autoclave, adds the 240g gac, airtight autoclave stirs liquid phase portion on one side, on one side with the interior gas phase portion of nitrogen replacement autoclave, cools off then that to make liquid phase portion be 5～10 ℃.Importing propylene to interior pressure in autoclave is 0.5MPaG, stirs 1 hour under 50 ℃ temperature then.Stop afterwards stirring, the pressure in the releasing reactor takes out reaction solution then.Filter out throw out under nitrogen gas stream from reaction solution, it is catalyst-loaded to obtain palladium.It is 10 quality % that the palladium of this catalyzer supports rate.
(reactor)
As reactor, use stirring grooved gas-liquid affixed the touch reactor of internal volume as 4L.This reactor has: can supply with continuously from the bottom of reactor the gas that contains molecular oxygen device, be used to make the pressure of the gas phase portion in the reactor to keep the constant compression force control device and the device of feeding liquid raw material continuously.In addition, formation can be discharged reaction solution under the liquid level constant situation that keeps liquid phase portion, and filtering catalyst is discharged to filtrate the outer structure of system then continuously.
(embodiment 1)
(the 1st oxidizing reaction)
The trimethyl carbinol aqueous solution that in this reactor, adds the 75 quality % of the catalyst-loaded and 2.5L of 264g palladium, then with nitrogen pressure to 4.8MPaG.The iso-butylene that in reactor, adds 250g, thus add the stock liquid that the iso-butylene of 25 mass parts modulates in the trimethyl carbinol aqueous solution of the 75 quality % that supply with in 100 mass parts continuously then, and to make its average retention time in reactor be 0.9 hour.At this moment, Yi Bian keep the interior liquid level of reactor, Yi Bian reaction solution is discharged, filtering catalyst is discharged filtrate then continuously.Then,, make the temperature of liquid phase portion be warming up to 90 ℃ simultaneously, begin reaction with 620NL/ hour speed continuously feeding air.Through after 91 hours, analyze the filtrate of discharging continuously after reaction beginning, the bearing reaction achievement is, isobutene conversion is 25.0%, and the Methylacrylaldehyde selection rate is 50.3%, and the methacrylic acid selection rate is 33.0%.This moment, the oxygen concn from reactor upper space part expellant gas was 4.3 capacity %.
In addition, use gas-chromatography to carry out the analysis of above-mentioned raw materials and resultant.The Methylacrylaldehyde of conversion for isobutene, generation and the selection rate of methacrylic acid are defined as follows:
Conversion for isobutene (%)=(B/A) * 100
The transformation efficiency of Methylacrylaldehyde (%)=(C/B) * 100
The selection rate of methacrylic acid (%)=(D/B) * 100
Here, A is the mole number of the iso-butylene of supply, and B is the mole number of the iso-butylene of reaction, and C is the mole number of the Methylacrylaldehyde of generation, and D is the mole number of the methacrylic acid of generation.
(stopping operation)
After above-mentioned oxidizing reaction finishes, stop air and supply with, the nitrogen of 5.7 times of amounts (0 ℃, 1 normal atmosphere) of the volume of the dispersion liquid that the catalyst-loaded dispersion of the palladium in the reactor is formed was with 620NL/ hour speed supply.In addition, the supply of stock liquid continues to supply with 1.0 hours after stopping air supply, stops then.At this moment, the oxygen concn from the upper space part expellant gas of reactor is 0.0 capacity %.Like this, operational safety in the time of can guaranteeing stopped reaction.
(the 2nd oxidizing reaction)
Then, carry out once more and the 1st time the identical oxidizing reaction of oxidizing reaction.Through after 91 hours, analyze the filtrate of discharging continuously after the reaction beginning, the bearing reaction achievement is, isobutene conversion is 25.5%, and the Methylacrylaldehyde selection rate is 43.5%, and the methacrylic acid selection rate is 33.8%.Like this, can prevent the deterioration of palladium supported catalyst.This moment, the oxygen concn from reactor upper space part expellant gas was 5.2 capacity %.
(comparative example 1)
(the 1st oxidizing reaction)
Implement oxidizing reaction according to method similarly to Example 1.
(stopping operation)
After above-mentioned oxidizing reaction finishes, stop the supply of air and stock liquid simultaneously, stopped reaction.At this moment, the oxygen concn from reactor upper space part expellant gas surpasses 6.0 capacity %, and further rises.Like this, the operational safety in the time of can not guaranteeing stopped reaction.
(the 2nd oxidizing reaction)
Then, carry out once more and the 1st time the identical oxidizing reaction of oxidizing reaction, the catalyst-loaded deterioration of palladium, the reaction achievement reduces.
Claims (9)
1. α, the preparation method of beta-unsaturated carboxylic acid, be by in reactor, in the presence of noble metal catalyst, with alkene or α, thereby beta-unsaturated aldehyde oxidation in liquid phase generates α, the oxidizing reaction of beta-unsaturated carboxylic acid prepares α, the method for beta-unsaturated carboxylic acid, it is characterized in that
Comprise that in above-mentioned reactor supplying with non-active gas makes the operation that stops that above-mentioned oxidizing reaction stops.
2. α as claimed in claim 1, the preparation method of beta-unsaturated carboxylic acid is characterized in that, supplies with alkene or α in reactor, beta-unsaturated aldehyde, solvent and molecular oxygen carry out above-mentioned oxidizing reaction continuously,
Stop in the operation above-mentioned, before supplying with non-active gas, stop the supply of molecular oxygen.
3. α as claimed in claim 2, the preparation method of beta-unsaturated carboxylic acid is characterized in that, stops in the operation above-mentioned, stops to supply with alkene or α, beta-unsaturated aldehyde after supplying with non-active gas.
4. as claim 2 or 3 described α, the preparation method of beta-unsaturated carboxylic acid is characterized in that, stops in the operation above-mentioned, and feed speed from non-active gas to reactor that supply with is 1～100 times of feed speed of supplying with molecular oxygen in above-mentioned oxidizing reaction.
5. as each described α of claim 1～4, the preparation method of beta-unsaturated carboxylic acid, it is characterized in that, stop in the operation that the cumulative volume of non-active gas under 0 ℃, 1 normal atmosphere that supplies in the reactor is 1～1000 times of amount of the reaction solution volume in the above-mentioned reactor above-mentioned.
6. as each described α of claim 1～4, the preparation method of beta-unsaturated carboxylic acid, it is characterized in that, stop in the operation that the cumulative volume of non-active gas under 0 ℃, 1 normal atmosphere that supplies in the reactor is 1～1000 times of amount of above-mentioned reactor volume above-mentioned.
7. as each described α of claim 1～6, the preparation method of beta-unsaturated carboxylic acid is characterized in that, stops in the operation above-mentioned, further supplies with reductive agent in above-mentioned reactor.
8. α as claimed in claim 7, the preparation method of beta-unsaturated carboxylic acid is characterized in that, above-mentioned reductive agent is to be liquid alkene or α, beta-unsaturated aldehyde under the temperature and pressure in reactor.
9. as claim 7 or 8 described α, the preparation method of beta-unsaturated carboxylic acid is characterized in that, stops in the operation above-mentioned, volume V[liter with the reaction solution in the reactor] be benchmark, the amount [gram] that supplies to the reductive agent in the reactor is V * 100～V * 2000.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP171890/2005 | 2005-06-13 | ||
| JP2005171890 | 2005-06-13 | ||
| PCT/JP2006/311710 WO2006134852A1 (en) | 2005-06-13 | 2006-06-12 | PROCESS FOR PRODUCING α, β-UNSATURATED CARBOXYLIC ACID |
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| CN101233096A true CN101233096A (en) | 2008-07-30 |
| CN101233096B CN101233096B (en) | 2012-02-01 |
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| US (1) | US20090299094A1 (en) |
| JP (1) | JP5016920B2 (en) |
| KR (1) | KR101306348B1 (en) |
| CN (1) | CN101233096B (en) |
| WO (1) | WO2006134852A1 (en) |
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| CN104011004A (en) * | 2011-12-29 | 2014-08-27 | 巴斯夫欧洲公司 | Preparation of alpha,beta-ethylenically unsaturated carboxylic salts by catalytic carboxylation of alkenes |
| US8962881B2 (en) | 2009-03-09 | 2015-02-24 | Nippon Shokubai Co, Ltd | Oxidized organic compound manufacturing method |
| CN105646196A (en) * | 2014-12-03 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method for preparation of 4-methylcyclohex-3-ene-1-carboxylic acid from 4-methyl-3-cyclohexene-1-carbaldehyde |
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| US8697909B2 (en) | 2011-12-29 | 2014-04-15 | Basf Se | Preparation of α,β-ethylenically unsaturated carboxylic salts by catalytic carboxylation of alkenes |
| MY169922A (en) * | 2012-10-01 | 2019-06-17 | Asahi Kasei Chemicals Corp | Method for stopping ammoxidation |
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| FR1576539A (en) * | 1968-05-21 | 1969-08-01 | ||
| US3792086A (en) * | 1971-11-10 | 1974-02-12 | Nat Distillers Chem Corp | Process for the preparation of acrylic and methacrylic acids |
| EP0375812A1 (en) * | 1988-12-23 | 1990-07-04 | Amoco Corporation | Process for the production of an aromatic polycarboxylic acid |
| DE4217718A1 (en) * | 1992-05-29 | 1993-12-02 | Bayer Ag | Process for the production of â, ß-unsaturated carboxylic acids |
| JP3276984B2 (en) * | 1992-06-19 | 2002-04-22 | 三菱レイヨン株式会社 | Supported catalyst for synthesis of unsaturated aldehyde and unsaturated carboxylic acid and method for producing the same |
-
2006
- 2006-06-12 JP JP2006522155A patent/JP5016920B2/en active Active
- 2006-06-12 KR KR1020087000896A patent/KR101306348B1/en active IP Right Grant
- 2006-06-12 US US11/917,422 patent/US20090299094A1/en not_active Abandoned
- 2006-06-12 CN CN2006800283786A patent/CN101233096B/en active Active
- 2006-06-12 WO PCT/JP2006/311710 patent/WO2006134852A1/en active Application Filing
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8962881B2 (en) | 2009-03-09 | 2015-02-24 | Nippon Shokubai Co, Ltd | Oxidized organic compound manufacturing method |
| CN104011004A (en) * | 2011-12-29 | 2014-08-27 | 巴斯夫欧洲公司 | Preparation of alpha,beta-ethylenically unsaturated carboxylic salts by catalytic carboxylation of alkenes |
| CN104011004B (en) * | 2011-12-29 | 2016-04-20 | 巴斯夫欧洲公司 | α is prepared, β-ethylenically unsaturated carboxylic acids salt by catalysis carboxylation alkene |
| CN105646196A (en) * | 2014-12-03 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method for preparation of 4-methylcyclohex-3-ene-1-carboxylic acid from 4-methyl-3-cyclohexene-1-carbaldehyde |
| CN105646196B (en) * | 2014-12-03 | 2018-02-23 | 中国科学院大连化学物理研究所 | A kind of method that the carboxylic acid of 4 methyl cyclohexane, 3 alkene 1 is prepared to methyl cyclohexane cyclohexene carboxaldehyde |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080027342A (en) | 2008-03-26 |
| CN101233096B (en) | 2012-02-01 |
| JPWO2006134852A1 (en) | 2009-01-08 |
| US20090299094A1 (en) | 2009-12-03 |
| WO2006134852A1 (en) | 2006-12-21 |
| JP5016920B2 (en) | 2012-09-05 |
| KR101306348B1 (en) | 2013-09-09 |
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